CN1181405A - Aqueous polish compositions containing acid-amine latexes - Google Patents
Aqueous polish compositions containing acid-amine latexes Download PDFInfo
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- CN1181405A CN1181405A CN97116064A CN97116064A CN1181405A CN 1181405 A CN1181405 A CN 1181405A CN 97116064 A CN97116064 A CN 97116064A CN 97116064 A CN97116064 A CN 97116064A CN 1181405 A CN1181405 A CN 1181405A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
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- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Disclosed is the use of film-forming acid-amine latexes in aqueous polish compositions whereby the resulting film is durable, tough, and resistant to detergent, but amine-strippable. Such polish compositions are metal-free and contain relatively low levels of volatile organic compounds.
Description
The present invention relates to ambient temperature curable, film-formable acid-amine latexes composition.These latex compositions contain the volatile organic matter of low levels, can be made into the dry film with good resistivity and weather resistance.More particularly, but rumbling compound and coating composition that latex composition processability of the present invention is improved, as the dirty seal of anti-heel and anti-scratch and resistant damage property.Rumbling compound and the coating composition that is made by latex composition of the present invention also has and similar resistance to detergents of the aqueous-based polymers of common metal ionomer and removability energy in addition.
In rumbling compound and application of paints, weather resistance, toughness and resistance to detergents are very important performance characteristics, and they must reach balance with easy removability.Past is to adopt the crosslinked polymkeric substance (metal corsslinking polymkeric substance) of transition metal composite to keep this equilibrated.The polymkeric substance of these types can be mixed with single component rumbling compound and coating system easily.But if consider, in coating that is combined with these type polymers or polishing agent combination, use heavy metal linking agent and quite high-load volatile organic matter, then can offset the advantage of these metal corsslinking polymkeric substance from environmental.
Given this, many nonmetal crosslinked aqueous-based polymers that are used for coating and polishing agent combination are developed.But up to the present, the general effect of used these polymkeric substance can not show a candle to the effect that adopts the metal corsslinking polymkeric substance to be reached in coating and rumbling compound application.Sole exception be the specific multicomponent system that adopts these nonmetal cross-linked polymers, they can reach and the effect that adopts the metal corsslinking polymkeric substance to be equal to.But the disadvantage that adopts multicomponent system is except making last user must mix two kinds of components before using coating or polishing agent combination mutually at least, and because the enough removabilities of coating shortage of gained make these systems can not be applied in practice.
For the resistance to detergents and the removability of nonmetal crosslinked single component aqueous-based polymers, U.S. Pat 5,428,107 (Tysak etc.) disclose a kind of solution.The disclosed coating composition of this patent contains the polymkeric substance monomer preparation, that have acetoacetate groups and carry out aftertreatment with the silane of amino functional that a kind of usefulness has acid function group.Though this composition can be used to prepare resistance to detergents and removability and reaches well balanced weather resistance and do not have zinc paint, it still contains considerable volatile organic matter.
U.S. Patent application SN07/464,844 (on February 12nd, 1996 application, Gray etc.), resistance to detergents and the removability to nonmetal crosslinked single component aqueous-based polymers provided another kind of solution.Gray etc. disclose a kind of metal-free coating composition, and it is crosslinked and contain alternative expansible emulsion polymer functional group before film forming.Though this composition can be used to prepare wash resistant agent and removability and reaches well balanced weather resistance and do not have zinc paint, it also contains considerable volatile organic matter.
The present invention relates to a kind of peelable, detergent-resistant water base polishing composition of amine that contains acid-amine latexes, said latex has self-crosslinking, self-vulcanizing and film-formable characteristics, in monomeric gross weight, the total amount of the acid functional group that latex contains is 0.5-12.5wt%, and the total amount of amine functional group is 1.0-22.5wt%.
The preferred latex wherein of these compositions of the present invention does not contain multivalent metallic ion crosslinking agent, and the preferred wherein content of volatile organic matter is 8wt% or lower.
The invention still further relates to a kind of method that improves dirty seal property of the anti-damageability of floor substrate, anti-scratch, anti-heel and scratch resistance, be included in and spread peelable, the detergent-resistant water base polishing composition of amine of the present invention in the substrate and composition is solidified and form layer protecting film.
In this manual, unless clearly be illustrated in addition in the literary composition, following term has following implication." latex " or " latex composition " is meant the dispersion of the insoluble polymer that can prepare by common polymerization process, and " resin " is meant the polymkeric substance in the latex." acid-amine polymer " or " acid-and amino-functionalization polymkeric substance " is meant the polymkeric substance that contains acid and amine functional group simultaneously; And " acid-amine latexes " or " acid-and amino-functionalization latex " is meant in the particle but must is not to constitute the latex that each polymer chain of particulate contains acid and amine functional group simultaneously." diamines " is meant the compound that contains at least two amidos, therefore also comprises triamine and above amine." volatile organic matter " or " VOC " is meant that boiling point is lower than 250 ℃ organic compound arbitrarily under a normal atmosphere.The minimum film-forming temperature (MFFT) that " but film forming " coating composition is meaning composition at room temperature or be lower than room temperature, makes polymkeric substance to melt and form the successive film.The commutative each other use of " rumbling compound " and " coating " two speech unless otherwise specified, refers to rumbling compound, coating composition or two kinds of compositions.The abbreviation of using has: the ml=milliliter; The g=gram; The Tg=second-order transition temperature; The eq=equivalent.Unless be specifically noted in addition, defined scope comprises cut off value.
The invention provides self-crosslinking, self-vulcanizing, film-formable acid-amine latexes.When being used to prepare polishing agent combination, these acid-amine latexes have improved performance, as the dirty seal of resistance to detergents, anti-heel with scrape scratch and traumatic resistance.These acid-amine latexes also provide the coating composition with good removability.
But the acid-amine latexes that can be mixed with coating of the present invention or polishing agent combination comprises contain acid and the film forming of amine functional group, water dispersible polymkeric substance arbitrarily simultaneously in dispersed polymer beads.Though preferably contain acid and amine functional group (being acid-amine polymer) simultaneously in specific polymer chain, this point is also nonessential like this, as long as dispersed polymer beads contains two kinds of functional groups (being acid-amine latexes) simultaneously.The existing report of this acid amide-latex, as see U.S. Pat 3,404,114 (Snyder etc.) and US4,760,110 (Das).The content of these patents is quoted in this explanation hereby.
In monomeric total amount, the total amount of the acid functional group of existing acid-amine latexes is generally between 0.5-12.5wt%, preferably between 3-10wt%, particularly between 6.5-8.5wt% in latex.In monomeric total amount, the total amount of the amine functional group of existing acid-amine latexes is generally between 1.0-22.5wt%, preferably between 1.5-16wt%, particularly between 3-6wt% in latex.
The existence form of acid-amine latexes of the present invention can be single-stage or multistage particle.Multistage particle contains at least two kinds of mutual exclusive multipolymers, and they have following any one form configuration: nuclear/shell, nuclear/shell particle that nuclear is not sealed by shell fully; Nuclear/shell the particle that contains a plurality of nuclears; Ipn particle or the like, most of area of particle surface is occupied by at least a outer level, and particulate inside is occupied by level at least a.
Preferred acid-amine polymer obtains for those are reacted by the poly-acid anhydrides in specific diamines and the equivalent emulsion polymer, contains hydroxy-acid group and acid amides-amine groups in this emulsion polymer simultaneously.Wherein first amine is primary amine or does not have the sterically hindered secondary amine that second amine is tertiary amine or hindered secondary amine in these diamines.Amide moieties in acid amides-amine groups is by the primary amine of diamines or does not have the anhydride functional group reaction in hindered secondary amine end group and the emulsion polymer and produce.The tertiary amine of diamines or hindered secondary amine part and acid anhydrides Fails To Respond exist with its original form.The emulsion polymer that is contained acid functional group and amine functional group thus simultaneously.This preferred acid-amine polymer has in the application form of " preparation method who contains the acid and the polymer composition of amine functional group simultaneously " that apply for simultaneously with the present invention and further describes (the polymkeric substance called after of being applied for " Madle acid-amine polymer ").
These Madle acid-amine polymers generally prepare with the polyaddition reaction that free radical causes.Polyreaction is preferably carried out in water medium, but also can carry out in polarity or non-polar organic solvent or their mixed solvent.This polymerization process is known by those skilled in the art, therefore need not do further discussion; But here some improvements of being done in the inventive method are summed up.At first be with a kind of anhydride monomers and a kind of ethylenically unsaturated monomer copolymerization and generate anhydride polymer in suitable medium.Join alkali in the reaction system this moment, adds diamines immediately various components are reacted.Exist in reaction medium in the system of water or polar solvent, anhydride polymer is then by the attack of medium institute; Therefore must before anhydride polymer significantly decomposes, alkali and diamines be added.
In preparation Madle acid-amine latexes, especially preferred diamines comprises: N, N-dimethyl-ethylenediamine, aminopropyl morpholine, 3-dimethylaminopropylamine, triacetonediamine and N-butyl triacetonediamine.The mol ratio of diamines and acid anhydrides is that every mole of acid anhydrides is to 0.001-2 mole diamines.Preferred anhydride monomers is acrylic anhydride or methacrylic anhydride.In monomeric total amount, the amount of used anhydride monomers is 0.1-50.0wt% in polymerization.
In another embodiment of the invention, adopt and contain and to prepare self-crosslinking, self-vulcanizing, film-formable latex with the silane compound of the amino functional of the primary amine group of anhydride functional group's reaction in the polymkeric substance.The preparation method of the preparation method of this type polymer and Madle acid-amine polymer is similar.
Acid-amine latexes of the present invention can be allocated according to corresponding step according to its end-use, and these steps are known (as used composition and their ratio and addition manner) for the personnel that are familiar with allocating technology.According to practical application, in these compositions, can add additive, for example thickening material, dispersion agent, pigment, extender, filler, frostproofer, softening agent, adhesion promotor, coalescing agent, wetting agent, defoamer, tinting material, non-aldehyde radical biocide, soap-like matter and antiseize paste.
Testing method
The testing method of employing floor polishing agent industry standard contrasts test to the performance of polishing agent combination of the present invention.Used test substrate is an alkene based composition brick bat in all tests.
Dirty seal of anti-heel and scratch--the method for measuring dirty seal of anti-heel and scratch adopts the method described in " the communique 9-73 of chemical industry AEM " (Chemical Specialty ManufacturersAssociation Bulletin No.9-73), but replacement is wherein selected for use with commodity 2 with rubber boots " (5.08 centimetres) rubber hose.In addition, we subjectively do not estimate to the substrate of coating, but measure (the 6.45cm per square inch of the coat substrates have dirty seal of heel and scratch
2) number of the marking on the area.The dirty seal of heel is meant rubber on coating or the deposition trace that stays in the coating, and scratch is that coating itself is replaced, and causes partial glossiness reduction.The place that presses substrate at heel can produce scratch and the dirty seal of heel simultaneously; That is to say, when removing the dirty seal of heel, can stay scratch.
Glossiness--the method for measuring the polishing agent combination glossiness is seen " ASTM (American society for testing materials) (ASTM) standard annual report; the 15.04th volume; the 15th part; AST MD1455 process of measurement " (" Annual Book of ASTM Standard; Section15; Volume15.04, TestProcedure ASTM D1455).
But but recoatability--the method for measuring water-base emulsion floor polishing agent recoatability is seen " ASTM (American society for testing materials) (ASTM) standard annual report; the 15.04th volume; the 15th part; ASTMD3153 process of measurement " (" Annual Book of ASTM Standard; Section15; Volume15.04, TestProcedure ASTM D3153).
Water tolerance--measure the water-proof method of polishing agent combination and see " ASTM (American society for testing materials) (ASTM) standard annual report; the 15.04th volume; the 15th part; TM51 D1793 process of measurement " (" Annual Book of ASTM Standard; Section15; Volume15.04, TestProcedure TM51 D1793), estimate the water tolerance of coating composition with following scale:
Fabulous: anhydrous mark of coating or significantly damage
Fine: faint watermark
Good: film slightly turns white
Generally: film turns white, some foaming, peeling
Difference: the film completely destroy, obviously turn white, lose cohesive force
Resistance to detergents--the method for measuring resistance to detergents is seen " ASTM (American society for testing materials) (ASTM) standard annual report; the 15.04th volume; the 15th part; ASTM D3207 process of measurement " (" Annual Book of ASTM Standard, Section15, Volume15.04; TestProcedure ASTM D3207); but the washing composition testing liquid adopts 1/20 Forward (Forward , S.C.Johnson and sons, Inc.; Racine, water diluent WI).
Removability--the method for measuring the rumbling compound removability is seen " ASTM (American society for testing materials) (ASTM) standard annual report; the 15.04th volume; the 15th part; ASTM D1792 process of measurement " (" Annual Book of ASTM Standard; Section15; Volume15.04, TestProcedure ASTM D1792).
Anti-damageability--this test is to carry out with the method that a hard thing clashes into dry coating in shallow angle mode.In the embodiment that is provided, the object of bump is test operation person's nail.This test is a size of measuring the anti-damageability of coating, and coating is damaged the reduction that then causes its glossiness.After coating is coated in the substrate and it is solidified, applied substrate is placed on the solid surface as on the desktop, and knocks with operator's nail.Operator's nail remain parallel to the direction of coatingsurface and ballistic angle from the surface normal meter greater than 45 °, to increase coating by the possibility of cut.When different coating was compared, the important point was to be tested by same operator.This test design is come the difference of the relative anti-damageability of differential coating with following scale system:
The 1=visual inspection has scratch less than coating
2=only can see very slight scratch from several angles
3=can see slight scratch from any angle
4=scratch clearly
The 5=coating easily is damaged
The content of VOC--organic compound uses the weight percentage of the organic coalescing agent that adds in coating composition to represent.
Film-formability--on an alkene based composition brick bat, 0.4 gram coating composition is grown into the film of 4 inches (10.16 centimetres) with 2 inches (5.08 centimetres) wide blade spreaders (illustrating in as the ASTM (American society for testing materials) ASTMD1436 process of measurement) coating that has 0.008 inch (0.02 centimetre) slit.After spreading rumbling compound, brick bat is placed on the horizontal plane of 10 ℃ of refrigerators immediately.Estimate desciccator diaphragm with following scale:
Fabulous: flawless
Fine: slight Edge crack
Good: limited Edge crack
Generally: limited Edge crack and slight centre burst
Difference: edge and center are completed into crackle
Second-order transition temperature (Tg)--the second-order transition temperature of all polymkeric substance all is to measure with differential scanning calorimetry (DSC) in an embodiment, and used temperature rise rate is 20 ℃ of per minutes, and the Tg value is got the mid point of limited proportionality.
Following examples further specify all respects of the present invention, scope of the present invention are not produced any restriction.Unless stated otherwise, percentage composition is based on total solid weight percentage.Use following listed abbreviation in an embodiment:
BA=butyl acrylate MMA=methyl methacrylate
MAA=methacrylic acid ALMA=allyl methacrylate(AMA)
STY=vinylbenzene MAAn=methacrylic anhydride
The DMAEMA=dimethylaminoethyl methacrylate
The amino propyl ester of DMAPMA=dimethylaminoethyl acrylate methyl
Prescription below using in the coating composition in embodiment 6,9,14,17,20 and 23-25.The consumption of regulating water is so that solid content remains 20%, and compensates the difference of each latex solid content and coalescent dosage.Various compositions are listed in the table below in proper order by their interpolation:
Composition effect consumption
(wt％)
Diluent water 40.78
FC-129 (1%)
1Wetting agent 1.07
Kathon CG/ICP (1.5% biocide 0.03)
2
SWS-211
3Defoamer 0.02
The diethylene glycol ethyl ether coalescing agent has nothing in common with each other
6
Tributoxyethyl phosphate leveling auxiliary agent 1.65
Latex polymer (38%) excipient 43.52
AC-325N (35%)
4Polythene wax emulsion 2.63Epolene E-43N (40%)
5Polypropylene wax emulsion 2.30 compositions biospecific polymer/wax ratio: 90/10 composition solid content: 20wt%
3M company (Minneapolis, MN)
2.Rohm and Haas company (Philadelphia, PA)
3.Wacker Silicones company (Adrian, MI)
4.Allied-Signal company (Morristown, NJ)
5.Eastman Chemical company (Eastport, TN)
6. content is 0-8wt%, decides according to composition
Embodiment 1: nonmetal crosslinked water-based latex (comparison)
Under agitation in a solution of forming by sodium lauryl sulphate (SLS) solution and the 2600 gram deionized waters of 77 gram 28wt% concentration, add following monomer lentamente in turn, obtain the emulsive monomer mixture.
Monomer weight (gram) wt%*
BA 1981 28.00
MMA 2441 34.25
MAA 849 12.00
STY 1769 25.00
AIMA 53 0.75
* in monomeric gross weight
Be equipped with in the reactor of thermometer, condenser and agitator one, 176 gram 28% sodium dodecyl sulfate solutions and 5150 solution that restrain deionized waters are heated to 80-85 ℃.In the disposable whole adding reactors of the 164 above-mentioned monomer emulsion of gram, temperature transfers to 80-82 ℃.Then with the disposable adding of canned ammonium persulphate (APS) catalyst solution (41.5 gram APS are dissolved in the 200 gram water).The temperature rising is 3-5 ℃ within about 5 minutes, and reaction mixture outward appearance (color and opaqueness) changes, and shows that polyreaction begins.After heat release stops, residual monomers mixture and catalyst solution (20.7 gram APS are dissolved in the 600 gram deionized waters) are joined in the reactor together gradually.The speed of select adding makes the polyreaction institute liberated heat institute that can be cooled take away (2-3 hour).Cooling by necessity makes polymeric reaction temperature maintain 80-84 ℃.Behind reinforced finishing, wash the container and the raw material transfer limes of monomer mixture and catalyzer with water, and washings is added in the reactor.Material is cooled to room temperature, and being diluted to total solid content is 38%, regulates pH value and storage.Regulating pH value with ammonia/ammonium bicarbonate aqueous solution is 7.0-8.0, the viscosity stability of emulsion when improving storage, and compatible with other used composition when making emulsion polymer join in the coating composition with composition.
Embodiment 2: the water-based latex of metal corsslinking (comparison)
According to preparing a kind of latex with embodiment 1 described identical step, but do not add ALMA in composition, it is 38% that resulting polymers is not diluted to total solid content yet.Add zinc (0.5 equivalent) as divalent ion according to following mode.
The latex of 1000 grams among the embodiment 1 joined in one 2 liters the Glass Containers and be heated to 50 ℃.In the latex that has heated, add 50 gram polyoxyethylene (23) lauryl ethers and 36.7 gram zinc crosslinked/Synergist S-421 95 commodity (containing 15%ZnO), under 50 ℃, stirred the mixture 30 minutes.With latex cooling, filtration, obtain latex then with 0.5 equivalent zinc modification.The pH value of the polymkeric substance of the metal corsslinking of gained is 8.8, and total solid content is adjusted to 38%.
Embodiment 3: the acid anhydrides latex (comparison) that does not contain amine functional group
Under agitation in a solution of forming by the sodium dodecyl sulfate solution and the 2600 gram deionized waters of 77 gram 28wt% concentration, add following monomer lentamente in turn, obtain a kind of emulsive monomer mixture.
Monomer weight (gram) wt%*
BA 3688 52.0
MMA 2979 42.0
MAA 71 1.0
MAAn 355 5.0
* in monomeric gross weight
Be equipped with in the reactor of thermometer, condenser and agitator one, the solution that will contain 176 gram 28% sodium dodecyl sulfate solutions and 5150 gram deionized waters is heated to 85 ℃.In the disposable adding reactor of the 164 above-mentioned monomer emulsion of gram.Then with the disposable adding of canned ammonium persulphate (APS) catalyst solution (41.5 gram APS are dissolved in the 200 gram water).The temperature rising is 3-5 ℃ within about 5 minutes, and reaction mixture outward appearance (color and opaqueness) also changes, and shows that polyreaction begins.After heat release stops, residual monomers mixture and catalyst solution (20.7 gram APS are dissolved in the 600 gram deionized waters) are joined in the reactor together gradually.The speed of select adding makes the polyreaction institute liberated heat institute that can be cooled take away (2-3 hour).Cooling by necessity makes polymeric reaction temperature maintain 80-85 ℃.Behind reinforced finishing, wash the container and the raw material transfer limes of monomer mixture and catalyzer with water, and washings is added in the reactor.Material is cooled to 45 ℃, and to regulate pH value with ammonia/ammonium bicarbonate aqueous solution be 7.0, the viscosity stability of emulsion when storing to improve, and make emulsion compatible with other used when preparing emulsion polymer composition.The solid content of emulsion is 46%, and glass transition temperature Tg is 21 ℃, and it is cooled to room temperature.
Embodiment 4: acid-amine polymer (0.5 equivalent aminopropyl morpholine)
The consumption that contains amine functional compounds in these embodiments is with respect to every normal anhydride functional group's one-level/secondary amino group equivalent.
The latex of 100 grams among the embodiment 3 joined in 200 milliliters the container and be heated to 45 ℃.In the latex that has heated, add 1.43 gram Triton X-405 tensio-active agent (70%) (UnionCarbide, Inc.; Danbury, CT).Mixture was left standstill 5 minutes, in container, add 1.08 gram aminopropyl morpholines then.With reaction mixture stirring reaction one hour, heat in case of necessity so that temperature maintenance at 45 ℃.Then with reaction mixture cooling, filter, and dilute with water to obtain total solid content be 38% emulsion.
Embodiment 5: acid-amine polymer (1.0 equivalent aminopropyl morpholine)
Step according to embodiment 4 is implemented, but adds 2.15 gram aminopropyl morpholines in the latex of 100 gram embodiment 3.
Embodiment 6
Weather resistance and resistivity with the polymkeric substance prepared coating composition of embodiment 1-5 are compared.
The fabulous fabulous glossiness of performance embodiment 1* embodiment 2* embodiment 3* embodiment 4 embodiment 5VOC, 88000 film-formabilities, but 60 °/20 ° 68,/32 69,/34 66,/27 68,/30 68/30 recoatability got well the carefully dirty seal property of the fabulous general poor general anti-damageability 33543 anti-heels of the general fine fabulous fine removability of the fine detergent resistance of water-tolerant 0.5 0.6 1.5 0.4 0.2 anti-scratches 0.7 0.7 1.2 0.85 0.7 carefully
* compare
The result shows, with have same composition, no amine functional group composition is compared, the coating composition that obtains with acid amide polymkeric substance of the present invention is improved at aspect of performances such as the dirty seals of anti-damage, anti-scratch and anti-heel.
Embodiment 7: the acid anhydrides latex (comparison) that does not contain amine functional group
Step according to embodiment 3 is implemented, but the Tg of the polymkeric substance that the monomeric 47BA/42MMA/10MAAn/1MMA of consisting of obtains like this is 36 ℃.，
Embodiment 8: acid-amine polymer (1.0 equivalent aminopropyl morpholine)
The coating composition of embodiment 8 contains 1.0 normal aminopropyl morpholines.Step according to embodiment 4 is implemented, but adds 4.29 gram aminopropyl morpholines in the latex of 100 gram embodiment 7.
Embodiment 9
Weather resistance and resistivity to the composition of embodiment 7-8 carry out testing.Embodiment 7-9 shows employing than the higher monomer of embodiment 3-6 anhydride-functional mass contg; The fabulous fine fabulous glossiness of and the present composition is improved in weather resistance and resistivity aspect.Embodiment 7 is the comparative examples that do not contain amine. performance embodiment 1 embodiment, 2 embodiment, 7 embodiment 8VOC, 8800 film-formabilities, but the fine fine detergent resistance of water-tolerant is general fine to the fabulous general poor good anti-damageability 3343 anti-heel dirty print 0.7 0.7 1.0 0.7 anti-scratches 0.5 0.6 0.85 0 of fabulous good removability carefully for 60 °/20 ° 68,/32 69,/34 67,/31 66/27 recoatability
* compare
The result shows, with have same composition, no amine functional group composition is compared, the coating composition that the present invention contains anhydride functional group and amine functional compounds is improved at aspect of performances such as the dirty seals of anti-damage, anti-scratch and anti-heel.
Embodiment 10: acid-amine polymer (1.0 equivalent 3-
The aminopropyl methyldiethoxysilane)
The coating composition of embodiment 10 contains 1.0 normal 3-aminopropyl methyldiethoxysilane.Step according to embodiment 4 is implemented, but adds 2.85 gram 3-aminopropyl methyldiethoxysilane in the latex of 100 gram embodiment 7.
Embodiment 11: acid amide polymkeric substance (1.0 equivalent piperazine)
The composition of embodiment 11 contains 1.0 normal piperazines.Step according to embodiment 4 is implemented, but adds 0.64 gram piperazine in the latex of 100 gram embodiment 7.
Embodiment 12: acid-amine polymer (1.0 equivalent triethylene glycol diamine)
The composition of embodiment 12 contains 1.0 normal triethylene glycol diamine.Step according to embodiment 4 is implemented, but adds 1.1 gram triethylene glycol diamine in the latex of 100 gram embodiment 7.
Embodiment 13: acid-amine polymer (1.0 equivalent Methionin)
The composition of embodiment 13 contains 1.0 normal Methionins.Step according to embodiment 4 is implemented, but adds 1.09 gram Methionins in the latex of 100 gram embodiment 7.
Embodiment 14
Weather resistance and resistivity to the composition of embodiment 10-13 carry out testing.Embodiment 10-14 shows the anhydride polymer that employing is carried out aftertreatment through four kinds of different amine functional compounds; The fabulous fabulous fine glossiness of and the present composition is improved in weather resistance and resistivity aspect. performance embodiment 1* embodiment 2* embodiment 3* embodiment 10 embodiment, 11 embodiment, 12 embodiment 13VOC, 8802222 film-formabilities, but 68,/32 69,/34 66,/27 65,/29 66,/32 70/,340 65/2860 °/20 ° recoatabilities are got well the carefully fabulous general poor general general anti-damageability 3353444 anti-scratch 0.7 0.7 1.2 0.5 0.7 0.8 0.65 anti-heel dirty prints 0.5 0.6 1.6 0.6 0.85 0.75 0.7 of the general fine fabulous fine fine removability of the fine fine detergent resistance of water-tolerant carefully
* compare
The result shows that under the situation of not using volatile organic matter, the coating composition that the present invention contains anhydride functional group and amine functional compounds is improved at aspect of performances such as the dirty seals of anti-damage, anti-scratch and anti-heel.
Embodiment 15: the acid anhydrides latex (comparison) that does not contain amine functional group
Step according to embodiment 3 is implemented, but the monomeric 47BA/21STY/21MMA/10MAAn/1MMA that consists of.The Tg of the polymkeric substance that obtains like this is 37 ℃.
Embodiment 16: sour anhydride polymer (1.0 equivalent aminopropyl morpholine)
This latex contains 1.0 normal aminopropyl morpholines.Step according to embodiment 4 is implemented, but adds 4.29 gram aminopropyl morpholines in the latex of 100 gram embodiment 15.
Embodiment 17
Weather resistance and resistivity to the composition of embodiment 15-16 carry out testing.Embodiment 15-17 shows higher anhydride functional group's monomer and the cinnamic polymkeric substance of employing content; The fabulous fine fabulous glossiness of and the weather resistance of the present composition and resistivity aspect are improved.The coating composition of embodiment 15 is the comparative example that does not contain amine. performance embodiment 1* embodiment 2* embodiment 15* embodiment 16VOC 8833 film-formabilities, but 60 °/20 ° 68,/32 69,/34 70,/37 70/42 recoatability fabulous general poor good anti-damageability 3353 anti-scratch 0.7 0.7 1.2 0.7 anti-heel dirty prints 0.5 0.6 0.8 0.11 of the general fine fabulous fine removability of the fine fine detergent resistance of water-tolerant carefully
* compare
The result shows that the present invention contains the organic coating composition of anhydride functional group and amine functional compounds and low level of voltile and is improved at aspect of performances such as the dirty seals of anti-damage, anti-scratch and anti-heel.
Embodiment 18: the acid anhydrides latex (comparison) that does not contain amine functional group
Step according to embodiment 3 is implemented, but the monomeric 27BA/21STY/41MMA/10MAAn/1MMA that consists of.The Tg of the polymkeric substance that obtains like this is 80 ℃.
Embodiment 19: acid-anhydride polymer (1.0 equivalent aminopropyl morpholine)
This latex contains 1.0 normal aminopropyl morpholines.Step according to embodiment 4 is implemented, but adds 4.29 gram aminopropyl morpholines in the latex of 100 gram embodiment 18.
Embodiment 20
Weather resistance and resistivity to the composition of embodiment 18-19 carry out testing.Embodiment 18-20 shows; Adopts the higher anhydride functional group's monomer of content and adopts the Tg polymkeric substance more higher than front embodiment; The fabulous glossiness of and the present composition is improved in weather resistance and resistivity aspect.The coating composition of embodiment 18 is the comparative example that does not contain amine. performance embodiment 1* embodiment 2* embodiment 18* embodiment 19VOC 8844 film-formabilities, but 60 °/20 ° 68,/32 69,/34 68,/30 70/34 recoatability general fabulous general anti-damageability 3343 anti-scratch 0.5 0.7 0.7 0.35 anti-heel dirty prints 0.6 0.5 0.7 0.05 of fine carefully removability of the fine fine detergent resistance of water-tolerant carefully
* compare
The result shows that the present invention contains the organic coating composition of anhydride functional group and amine functional compounds and low level of voltile and is improved at aspect of performances such as the dirty seals of anti-damage, anti-scratch and anti-heel.
Embodiment 21: the acid anhydrides latex (comparison) that does not contain amine functional group
Step according to embodiment 3 is implemented, but the monomeric 27BA/21STY/41MMA/10MAAn/1MMA that consists of.This latex is mixed with subject composition as described in embodiment 19, but adopts 4 gram diethylene glycol ethyl ethers.
Embodiment 22: acid-amine polymer (1.0 equivalent N, N-dimethyl-ethylenediamine)
This latex contains 1 normal N, N-dimethyl-ethylenediamine.Step according to embodiment 4 is implemented, but adds 2.29 gram N, N-dimethyl-ethylenediamine in the latex of 100 gram embodiment 21.
Embodiment 23
Weather resistance and resistivity to the composition of embodiment 21-22 carry out testing.Embodiment 21-23 shows, adopts and contains anhydride functional group's monomer and carry out the polymkeric substance of aftertreatment with containing amine functional compounds, and the present composition is improved in weather resistance and resistivity aspect.The coating composition of embodiment 21 is the comparative example that does not contain amine.
Performance embodiment 1* embodiment 2* embodiment 21* embodiment 22
VOC 8 8 4 4
Film-formability is fabulous
Glossiness, 60 °/20 ° 68,/32 69,/34 68,/30 70/30
But recoatability carefully
Water-tolerant is fine fine
Resistance to detergents is general carefully fine
Removability is fabulous general poor
Anti-damageability 3343
Anti-scratch 0.5 0.7 0.7 0.4
The dirty seal property 0.6 0.5 0.7 0.08 of anti-heel
* compare
The result shows that the present invention contains the organic coating composition of anhydride functional group and amine functional compounds and low level of voltile and is improved at aspect of performances such as the dirty seals of anti-damage, anti-scratch and anti-heel.
Embodiment 24
The coating composition of embodiment 24 is according to U.S. Pat 4,760, the technology of 110 (Das) and a kind of not containing metal for preparing, the aqueous-based polymers of single component.Prepare a kind of polymer latex according to monomeric 50 (32BA/53MMA/15MAA) // 50 (15BA/75STY/10DMAEMA (dimethylaminoethyl methacrylate)) that consist of.This latex is mixed with subject composition as described in embodiment 22, but adopts 8 gram diethylene glycol ethyl ethers.Weather resistance and resistivity to the coating composition of embodiment 24 carry out testing.The results are shown in following table.
Performance embodiment 1* embodiment 2* embodiment 24
VOC 8 8 8
Film-formability is fabulous fabulous
Glossiness, 60 °/20 ° 68,/32 69,/34 70/32
But recoatability well carefully
Water-tolerant is fine
Resistance to detergents is general fine
Removability is fabulous general
Anti-damageability 333
The dirty seal property 0.5 0.6 0.35 of anti-heel
Anti-scratch 0.7 0.7 0.4* relatively
Embodiment 25
The coating composition of embodiment 25 is according to U.S. Pat 3,404, the technology of 114 (Snyder etc.) and a kind of not containing metal for preparing, the aqueous-based polymers of single component.Prepare a kind of polymer latex according to the monomeric 22BA/62.5MMA/10MAA/5DMAPMA of consisting of (the amino propyl ester of dimethylaminoethyl acrylate methyl).This latex is mixed with subject composition as described in embodiment 24, but adopts 8 gram diethylene glycol ethyl ethers.Weather resistance and resistivity to the coating composition of embodiment 25 carry out testing.The results are shown in following table.
Performance embodiment 1* embodiment 2* embodiment 25
VOC 8 8 8
Film-formability is fabulous fabulous
Glossiness, but well dirty seal property 0.5 0.6 0.3 anti-scratch 0.7 0.7 0.4* of the fabulous general good anti-damageability 332 anti-heels of the general fine good removability of the fine good resistance to detergents of water-tolerant are relatively carefully for 60 °/20 ° 68,/32 69,/34 65/28 recoatability
Claims (8)
1, a kind of peelable, detergent-resistant aqueous polish compositions of amine that contains self-crosslinking, self-vulcanizing, film-formable acid-amine latexes, in monomeric gross weight, it is the amine functional group of 1.0-22.5wt% that said latex contains acid functional group and the total amount that total amount is 0.5-12.5wt%.
2, the composition of claim 1, wherein in monomeric gross weight, latex contains the acid functional group of 3-10wt% and the amine functional group of 1.5-16wt%.
3, the composition of claim 2, wherein in monomeric gross weight, latex contains the acid functional group of 6.5-8.5wt% and the amine functional group of 3-6wt%.
4, the composition of claim 1, wherein acid-amine latexes contains the polymkeric substance that has acid and amine functional group that is generated by the polymerization process of following free radical initiation:
(a) at first, anhydride monomers and ethylenically unsaturated monomer copolymerization are generated anhydride polymer, wherein in monomeric gross weight, the consumption of anhydride monomers is 0.1-50.0wt%;
(b) to wherein adding alkali;
(c) add diamines immediately, add-on is every mole of acid anhydrides 0.001-2.0 mole diamines; And
(d) each component is reacted.
5, the composition of claim 1, wherein latex does not contain multivalent metallic ion crosslinking agent or its residue.
6, the composition of claim 1, wherein in the gross weight of composition, the content of volatile organic matter is 8wt% or lower.
7, the composition of claim 6, wherein the content of volatile organic matter is lower than 4wt%.
8, a kind of method that improves the dirty seal property of the anti-damageability of floor substrate, anti-scratch and anti-heel; be included in peelable, the detergent-resistant water base polishing composition of the amine that spreads in the substrate in the claim 1; and composition is solidified, in the substrate of this floor, form layer protecting film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2442396P | 1996-08-20 | 1996-08-20 | |
| US024,423 | 1996-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1181405A true CN1181405A (en) | 1998-05-13 |
Family
ID=21820516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116064A Pending CN1181405A (en) | 1996-08-20 | 1997-08-19 | Aqueous polish compositions containing acid-amine latexes |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6319977B1 (en) |
| EP (1) | EP0825240A3 (en) |
| JP (1) | JPH1088011A (en) |
| KR (1) | KR19980018696A (en) |
| CN (1) | CN1181405A (en) |
| AU (1) | AU733839B2 (en) |
| BR (1) | BR9704475A (en) |
| CA (1) | CA2212407A1 (en) |
| MX (1) | MX9706354A (en) |
| ZA (1) | ZA977244B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412152C (en) * | 2002-01-18 | 2008-08-20 | 卡伯特微电子公司 | CMP systems and methods utilizing amine-containing polymers |
| CN104159986A (en) * | 2012-03-06 | 2014-11-19 | 威士伯采购公司 | Latex polymer for improved paint washability |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1547573B1 (en) * | 2003-12-22 | 2007-02-14 | Rohm And Haas Company | Aqueous nail varnish with fast drying properties |
| DE602004004734T2 (en) * | 2003-12-22 | 2007-10-31 | Rohm And Haas Co. | Water-based nail polish with quick-drying properties |
| US20060198801A1 (en) * | 2005-03-03 | 2006-09-07 | Yves Duccini | Aqueous nail varnish with improved film properties |
| US20060205865A1 (en) * | 2005-03-10 | 2006-09-14 | Omnova Solutions, Inc. | High solids latex for dry-bright floor polish compositions |
| US20080264445A1 (en) * | 2006-10-24 | 2008-10-30 | Ecolab Inc. | System and method for treating floors |
| CN109689807B (en) | 2016-10-05 | 2022-10-11 | 罗门哈斯公司 | Acrylic polymers neutralized with amino alcohols |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404114A (en) | 1965-06-18 | 1968-10-01 | Dow Chemical Co | Method for preparing latexes having improved adhesive properties |
| US3984299A (en) | 1970-06-19 | 1976-10-05 | Ppg Industries, Inc. | Process for electrodepositing cationic compositions |
| DE2417172A1 (en) * | 1973-04-13 | 1974-10-31 | Procter & Gamble | POLISHING AND CLEANING AGENTS |
| DE2732851A1 (en) | 1977-07-21 | 1979-02-08 | Bayer Ag | USE OF POLYIMIDAMINE SALT AS A CATIONIC SURFACE SIZE FOR PAPER |
| US4166882A (en) | 1978-04-26 | 1979-09-04 | Ppg Industries, Inc. | Method of coating with aqueous thermosetting acrylic polymer latex of uniform particle size |
| US4414360A (en) * | 1981-04-13 | 1983-11-08 | Purex Corporation | Spray buff reactant and application thereof |
| US4760110A (en) * | 1987-04-06 | 1988-07-26 | Ppg Industries, Inc. | Process for preparing anionic acrylic latex compositions |
| DE4133123A1 (en) | 1991-10-05 | 1993-04-08 | Basf Ag | USE OF COPOLYMERISATES FROM LONG-CHAIN OLEFINS AND MALEINIC ACID ANHYDRIDE IN THE FORM OF HALBAMIDES WITH MORPHOLINE AS A SIZING AGENT FOR PAPER |
| US5391624A (en) * | 1992-02-10 | 1995-02-21 | S. C. Johnson & Son, Inc. | Thermosettable compositions |
| AT396934B (en) * | 1992-02-14 | 1993-12-27 | Vianova Kunstharz Ag | METHOD FOR THE PRODUCTION OF AQUEOUS, SELF-CROSSLINKING POLYMER DISPERSIONS AND THEIR USE AS A BINDING AGENT FOR STORAGE-COMPONENT VARNISHES |
| US5428107A (en) * | 1993-10-29 | 1995-06-27 | Rohm And Haas Company | Silane-modified floor finish vehicles |
| DE69604544T2 (en) * | 1995-07-21 | 2000-07-06 | Rohm & Haas | Processes to improve the drying speed in the printing process and quick-drying printing inks for this purpose |
| US5693732A (en) * | 1996-01-08 | 1997-12-02 | Gencorp. Inc. | Latex binder for paper coating formulations having improved strength and blister resistance |
-
1997
- 1997-08-06 AU AU33175/97A patent/AU733839B2/en not_active Ceased
- 1997-08-06 CA CA002212407A patent/CA2212407A1/en not_active Abandoned
- 1997-08-13 ZA ZA9707244A patent/ZA977244B/en unknown
- 1997-08-14 KR KR1019970038878A patent/KR19980018696A/en not_active Application Discontinuation
- 1997-08-15 EP EP97306227A patent/EP0825240A3/en not_active Withdrawn
- 1997-08-15 US US08/911,974 patent/US6319977B1/en not_active Expired - Fee Related
- 1997-08-19 CN CN97116064A patent/CN1181405A/en active Pending
- 1997-08-20 JP JP9239076A patent/JPH1088011A/en not_active Withdrawn
- 1997-08-20 MX MX9706354A patent/MX9706354A/en unknown
- 1997-08-20 BR BR9704475A patent/BR9704475A/en active Search and Examination
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412152C (en) * | 2002-01-18 | 2008-08-20 | 卡伯特微电子公司 | CMP systems and methods utilizing amine-containing polymers |
| CN101318309B (en) * | 2002-01-18 | 2010-07-14 | 卡伯特微电子公司 | CMP systems and methods utilizing amine-contained polymer |
| CN104159986A (en) * | 2012-03-06 | 2014-11-19 | 威士伯采购公司 | Latex polymer for improved paint washability |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0825240A2 (en) | 1998-02-25 |
| KR19980018696A (en) | 1998-06-05 |
| US6319977B1 (en) | 2001-11-20 |
| JPH1088011A (en) | 1998-04-07 |
| BR9704475A (en) | 1999-01-12 |
| AU733839B2 (en) | 2001-05-24 |
| CA2212407A1 (en) | 1998-02-20 |
| MX9706354A (en) | 1998-02-28 |
| ZA977244B (en) | 1998-02-23 |
| AU3317597A (en) | 1998-02-26 |
| EP0825240A3 (en) | 1998-06-17 |
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